TW527740B - Fluoroalkylphosphate salts, and process for the preparation of these substances - Google Patents

Abstract

The present invention relates to fluoroalkylphosphate salts and to a process for their preparation. The present invention furthermore relates to mixtures which comprise the fluoroalkylphosphate salts according to the invention, and to the use of these salts or these mixtures in electrolytes, primary batteries, secondary batteries, capacitors, supercapacitors or galvanic cells.

Description

527740 A7 B7 5. Description of the invention (1) The present invention relates to a fluoroalkyl phosphate and a method for preparing the same. The present invention also relates to the mixtures containing the fluorine-based base-based phosphates according to the present invention and these mixtures (please read the precautions on the back before filling out this page). The compounds are used in electrolytes, primary batteries, batteries, capacitors or electrolytic cells. 〇 Use of portable electronic equipment (such as: laptop and palmtop computers, mobile phones or camcorders) is widely used, so in recent years the world's demand for lightweight and high-performance batteries is growing. In view of the current rising requirements for batteries and related ecological issues, the development of long-life rechargeable batteries is becoming increasingly important. In the early 1990s, rechargeable lithium-ion batteries were available on the market. Most of these batteries use lithium hexafluorophosphate as the conductive salt. However, this lithium salt is a compound that is quite sensitive to the hydrolysis reaction and has low thermal stability. Therefore, the related lithium battery can only be manufactured in a very complicated and therefore very expensive manner due to the nature of these salts. In addition, this sensitivity reduces the life and performance of these lithium batteries, and also impairs their use under extreme conditions (such as local temperature). For these reasons, lithium perfluoroalkylfluorophosphate, which has better chemical and electrochemical stability and better discharge performance than the conventional L 1 P F 6, has been developed for use in lithium batteries as conductive salts in high-energy lithium battery electrolytes. The highly hydrolytic stability of lithium perfluoroalkyl fluorophosphate has led to interest in their use as powerful lithium batteries in electric vehicles (M. Schmidt, U. Hrider, A. KCihner, R. Oesten, M. Jungnitz, N .Ignat 'ev, P.Sartori. J.of Power Sources (Accepted), W 〇 9 8/1 5 5 6 2 (Mack KGaA), P 100 08 955.0 (Merck KGaA), N.Ignat' ev and P Sartori, J. of Fluroine Chem., 101 (2000), p. 203-207). These paper sizes are in accordance with Chinese National Standard (CNS) A4 specifications (210X 297 mm) * 4-527740 A7 ____ B7 V. Description of the invention (2) The disadvantages of the substances are their high molecular weight and the resulting L i + cation content / Low conductive salt per unit weight. (Please read the notes on the back before filling this page) Therefore, the object of the present invention is to propose a stable conductive salt with a higher cation content / unit weight. Another object of the present invention is to improve the service life and efficiency of primary and livestock batteries, power valleys, ultracapacitors and / or electrolytic cells. Ken b. With the novel fluoroalkyl phosphate of general formula (I), the invention (MaT) D [(CnF2n + l-mHn1) yPF5-y (CRlR2) xPF5-y (CnF2n + l-mHm) y) U- ju.b / 2) (I) where M a τ is a monovalent, divalent, or trivalent cation, a = 1, 2, 2 or 3, when a 2 is 1, b 2 and a = 3, b = 2, when a = 2, b = 1, in each case printed by the Industrial and Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs, 1 ^ η ^ 8, when η = 1 or 2, 0 gm S 2, 3 S n S 8 〇 S m S 4, 1 ^ x ^ 1 2, 0 ^ y ^ 2, R ^ and R 2 are the same or different, and are selected from fluorine, hydrogen, alkyl, fluoroalkyl, and the paper standards are applicable to Chinese national standards (CNS) A4 specification (210X297 mm) -5- 527740 A7

Perfluoroalkyl substituents, and the substituents (C n F 2 n + i-m H m) in each case are the same or different. In a preferred case, in the fluoroalkyl phosphate of the general formula (I) according to the present invention, M a + is an alkali metal cation, preferably lithium, sodium or potassium ions, particularly preferably lithium cations or magnesium or aluminum. cation. Therefore, in a preferred case, the cation M a + in the fluoroalkyl phosphate of the general formula (I) is an organic cation, preferably a nitrosyl cation, a nitrosyl cation or the general formula [N (R 7 ) 4] +, [p (R 7) 4]-, [P (N (R 7) 2) 4] ten or [C (N (R 7) 2) 3] ten cation, among which in each case The groups R 7 are the same or different and are Η,

Alkyl (C

C or A, where any fluorene atom in the alkyl chain may be substituted with fluorine or any aryl group (containing heteroatoms as appropriate) or cycloalkyl (preferably 5-6 members), and / or alkane The C atom in the base chain may be replaced by a heteroatom (preferably oxygen). Aromatic or cycloaliphatic radicals A may optionally contain heteroatoms, and may be »suitable for the preparation of [N (R 7) 4] + known to those skilled in the art, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [P (R 7) 4] ten, [P (N (R 7) 2) 4] + or [C (N (R 7) 2) 3] + any aromatic, heteroaromatic or _ aliphatic Group. In each case, the preferred A is a 5- or 6-membered aryl group (which optionally contains nitrogen and / or sulfur and / or oxygen atoms) or a cycloalkyl group (preferably having 5 or 6 #), particularly Preferred is phenyl or pyridyl. In another preferred embodiment of the present invention, the cation M a " is a heteroaromatic risk paper size and is applicable to Chinese National Standard (CNS) A4 specifications (21〇χ 297 mm) -6- 527740 A7 B7 V. Invention Note (4) an ion selected from heteroaromatic cations including the general formulae (Π) to (IX)

This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 527740 Α7 Β7 V. Description of the invention (5)

N—N

(Please read the notes on the back before filling out this page) (Fluorine is preferred) or Ci-8 courtyard, which can be optionally substituted by f, C1, .N (CrF (2r + ls) Hs ) 2, 〇 (CrF (2 r + 1-s) H s) 2, S 〇2 (C r F (2 r + 1-s) H s) or C r F (2 r + 1-s) H s household replacement, of which l'r $ 6 and 〇ss ^ l3. Both of the groups R to R6 can also be combined into a C ι-s-courtyard, which may optionally be substituted by the groups F, C 1, N (C r F (2 r + 1-s) H s) 2 〇 (CrF (2 r + 1-s) H s) 2, S〇2 (CrF (2r + ls) Hs) 2 or CrF (2r + ls) Hs Instead, where 1 $ r S 6 and 0 $ s S 2 r + 1. It should be noted that if the groups R 1 to R 6 are directly connected to nitrogen, the groups R 1 to R 6 in the heteroaromatic cations of the general formulae (Π) to (IX) cannot be halogen. Among the preferred chloride salts of general formula (I), 1 $ n $ 6 is preferred, and 1 ′ η $ 3 is preferred. Among the preferred fluoroalkyl phosphates of the general formula (I), 1 ′ X $ 8 is preferred, and 1 S X $ 4 is preferred. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -8- 527740 A7 B7 V. Description of the invention (6) Among the fluoroalkyl phosphates of general formula (I), m20 is particularly good. Among the fluoroalkyl phosphates of the general formula (I), y is 2 or 2. (Please read the notes on the back before filling out this page.) In the fluoroalkyl phosphates of the general formula (I) according to the present invention, R 1 and R 2 are chlorine. Particularly preferred fluoroalkyl phosphates of formula (I) are: (Lr) 2 [(C2F5) 2PF3 (CF〇2PF3 (C2F5) 2] i2-; and (N (C2H5) 〇2 [(C2F5) 2PF3 ( CF〇2PF3 (C2F〇2) (2-) The fluoroalkyl phosphates of the general formula (I) according to the present invention can be used as electrolytes, primary and secondary batteries, capacitors, supercapacitors and / or electrolytic cells in pure form or as a mixture thereof. The conductive salt in .The salt according to the present invention is used as the electrolyte in a pure form, because at this time it is ensured that the electrochemical properties have particularly good reproducibility. However, the salt according to the present invention can also be known to those skilled in the art Mixed salts of other salts are used as conductive salts. They are printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and they can be used in proportions between 1 and 99% with other conductive salts used in electrochemical cells. Where appropriate, select From L 1 PF 6, LiBF4, LiCl〇4, LiAsF6, L 1 CF 3 S 〇3, L i N (CF 3 S 〇2) 2, L 1 N (CF: 3 CF 2 S 〇2) 2, L i C (CF 3 S 0 2) 3 or a conductive salt C of lithium fluoroalkyl phosphate having the general formula L 1 [PF c 6.) (C d F 2 d + 1)] wherein 1 ^ 5 and 5 1 $ ^ 1 $ 8 ) And L 1 N "S 〇2 (C e F 2 e + i)] 2. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -9- 527740 A7 B7 grams, invention description (7 ) L 1 CS Ο 2 (. C e F 2 e + 1) 3 and L 1 [S〇3 (CeF2e + i)] (where 2 S e S 8) and (Please read the notes on the back before filling (This page) their mixtures. The salts of formula (I) and their mixtures can be similarly used in the electrolyte of an electrolytic cell. This electrolyte can also contain organic isocyanates (DE 199 44 603, described herein) This is incorporated by reference) to reduce the water content. The present invention also relates to a method for preparing a fluoroalkyl phosphate according to the present invention. In this method, at least one kind of fluorine-α, ω-bis [(fluoroalkyl) fluoro Phospho] alkane reacts with at least one fluorine salt of the general formula (X) in a solution (M a ") [F-] a (X) where (M a 丨) is as defined above, and the general formula according to the present invention is obtained. A fluoroalkyl phosphate of formula (I), which can be suitably purified and / or separated by customary methods. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the formula according to the present invention. In a preferred embodiment, the fluorine-αω-bis [(fluoroalkyl) fluorophosphino] ane used is at least one compound of the general formula (χ I) (C Π F 2 η + 1-m H m) y PF 4- y (CR 1 R 2): < PF 4-y (C n F 2 n + i-m H m) y (XI) where 1 S n S 8, and n = 1 or 2, 〇S m S 2, 3 This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -10- 527740 A7 B7 V. In the description of the invention (8), 0Sm $ 4, 1 ^ x ^ 1 2, 0 ^ y ^ 2,

Ri and R2 are the same or different and are selected from fluorine, hydrogen, alkyl, fluoroalkyl, and perfluoroalkyl substituents, and (please read the precautions on the back before filling this page) in each case, the substituent (C n F 2 η + 1-m H m) y are the same or different. According to the method of the present invention, it is preferable that the compound of the general formula (X) exceeds 10 times (by no more than 5) the amount of fluorine-α, ω-bis [(fluorine-based) fluorophosphorus] based on the weight. Times better, especially no more than 2 times). In the best case, the compound of the general formula (X) is used at twice the amount of fluorine-α, ω-[(fluorine-based) fluorine / fluorine]. In the method according to the present invention, the reaction temperature for the reaction with the fluorine salt of the general formula (X) is preferably from 35 to + 80 ° C, preferably from 20 to +50 t, especially from 1 to 1. 0 to 2 5 ° C. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Industrial Cooperative Cooperative, suitable solvents are organic carbonates (using ethylene carbonate, propylene carbonate, butyl carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid Methyl ethyl ester or methyl propyl carbonate is preferred), organic esters (such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, Ethyl butyrate or τ-butyrolactone), organic ether (preferably diethyl ether, dimethoxyethane or diethoxyethane), organic ammonium amine (dimethylformamide or Dimethylacetamide is preferred), sulfur-containing solvents (preferably dimethylmethylene, dimethylsulfide, diethylsulfide, or propionium), aprotic solvents (acetonitrile, acrylonitrile, propionitrile, or acetone) Preferably) or at least partially fluorinated derivatives of the foregoing solvents or a mixture of at least two of these solvents and / or fluorinated derivatives of these solvents. This paper size applies the Chinese National Standard (CNS) A4 specification (21 0X 297 mm) -11-527740 A7 _____B7 V. Description of the invention (9) The fluoroalkyl phosphate according to the general formula (I) of the present invention is also applicable In solid electrolyte. For the purposes of the present invention, a solid electrolyte refers to a polymer electrolyte (which usually contains a crosslinked polymer and a conductive salt) and a colloidal electrolyte (in addition to the parent polymer and conductive salt, usually contains at least one solvent ). Accordingly, the present invention further relates to a mixture comprising: a) at least one fluoroalkyl phosphate of general formula (I), and b) at least one polymer. For the purposes of the present invention, this mixture encompasses a pure mixture of components a) and b), the salt of component a) contains a mixture of components] ^) polymers, and the salts and components of component a) b) A mixture in which chemical and / or physical bonds are present between the polymers. In a preferred embodiment of the invention, the mixture according to the invention comprises 5 to 90% by weight of component a) and 95 to 5% by weight of component b), in particular 10 to 80% by weight of component a ) And 90 to 20% by weight of component b). The weight ratios described in each example are based on the sum of components a) and b). As regards b), the mixture according to the invention comprises homopolymers or copolymers of acrylonitrile, vinylidene difluoride, methyl (meth) acrylate, tetrahydrofuran, ethylene oxide, siloxane, and phosphazane It is preferably a mixture of at least two of the above-mentioned homopolymers and / or copolymers. A particularly preferred component b) is a homopolymer or copolymer of vinylidene difluoride, acrylonitrile, methyl (meth) acrylate or tetrahydrofuran, and a very preferred one is a homopolymer or copolymer of vinylidene difluoride. . Homopolymers and copolymers suitable for vinylidene fluoride are sold on the market. The name is ^ Paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) ---- -12- (Please read the back first Please note this page before filling in this page) 1 ··· 11 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives 527740 A7 B7 V. Description of Invention (10)

Kynai.® and Kynai.fle; i® (At〇nna Chemicals, Inc.,) and Solef® (Solvay) 〇 (Please read the notes on the back before filling this page) The polymer used according to the present invention can also be used Is at least partially cross-linked. This cross-linking can be carried out using known cross-linking agents by conventional methods known to those skilled in the art. In addition to the fluoroalkyl phosphates and polymers of the general formula (I), the mixtures according to the invention may also comprise a solvent or a solvent mixture of two or more solvents. The Intellectual Property Office of the Ministry of Economic Affairs 3 (The best solvent for industrial and consumer cooperatives is organic carbonate (based on ethylene carbonate, propylene carbonate, butyl carbonate, dimethyl carbonate, diethyl carbonate, methyl carbonate Ester ethyl ester or methyl propyl carbonate is preferred), organic esters (methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, butyric acid Ethyl or r-butyrolactone), organic ether (preferably diethyl ether, dimethoxyethyl or diethoxyethane), organic ammonium (dimethylformamide or dimethylamine) Acetylamine is preferred), sulfur-containing solvents (preferably dimethylmethylene, dimethylsulfide, diethylsulfide or propionate), aprotic solvents (preferably acetonitrile, acrylonitrile, propionitrile or acetone) ) Or at least partially fluorinated derivatives of the foregoing solvents or a mixture of at least two of these solvents and / or fluorinated derivatives of these solvents. The invention further relates to at least one fluoroalkyl phosphate according to the invention Use in electrolytes, primary batteries, accumulators, capacitors, supercapacitors and / or electrolytic cells If necessary, it can also be used with other known conductive salts and / or additives. The invention relates to electrolytes, primary batteries, accumulators, capacitors, ultra-thin paper standards applicable to China National Standard (CNS) A4 specifications (210 X 297 Publicly available;) -13-527740 A7 B7 V. Description of the invention (11) Electric valley and / or electrolytic cell containing fluoroalkyl phosphate according to the general formula (I) of the present invention or according to the present invention and optionally And the use of other conductive salts and / or additives mixtures. Other conductive salts and additives are known to those skilled in the art, such as: Dor on Auerbach, No naqueous Electrochemistry, Marc Dekker Inc.? New York 1 999; D. Linden, Handbook of Batteries, 2nd Ed., McGraw-Hill Inc., New York 1995, and G. Mama ntov and AIPopov, Che mist l. Y of No naqueous Solutions, Current Progress, VCH Verlagsgesellschaft, Weinheim 1994. The above-mentioned ones are hereby incorporated by reference. The electrolyte according to the present invention has a fluoroalkyl phosphate concentration of from 0.01 to 3 moles / liter, preferably from 0.01 to 2 moles / liter, 0.1 to 1.5 mol / liter As for the solvent used for the salt according to the present invention, the electrolyte contains organic carbonate (as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl carbonate, etc.). Ester or methyl propyl carbonate is preferred), organic esters (using methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate Or r ~ butyrolactone), organic ether (preferably diethyl ether, dimethoxyethane or diethoxyethane), organic ammonium amine (dimethylformamide or dimethylethyl) Phenylamine is preferred), sulphur-containing solvent C is preferably dimethylmethylene, dimethylsulfide, diethylsulfide or propionium), aprotic solvents (preferably acetonitrile, acrylonitrile, propionitrile or acetone) At least partially fluorinated derivatives of the foregoing solvents or mixtures of at least one of these solvents and / or gasified derivatives of these solvents. (Please read the precautions on the back before filling in this page) Γ i-Ichikou Intellectual Property Bureau of the Ministry of Economy g (printed paper printed by the Industrial and Consumer Cooperatives A Ns c quasi-standard home country and national government use appropriate centimeter 4 527740 A7-~ ~ -— _ B7 _ i 'Explanation of the invention (13) L ^ N (CF 3 S Ο 2) 2 > L 1 N (CF 3 CF and L i C (CF 3 S〇2) 3 and mixtures thereof. This electrolyte may also contain organic isocyanates (DE 1 9 9 4 4 6 0 3) to reduce the water content c. There may also be compounds of the general formula CDE 9 9 4 1566) 2 S〇 [([R1 (CR2R3) k] ， Ax) yKt] + * N (CF3): {Please read the notes on the back before filling in this page. J Printed by W Industry Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economy, Kt = N, P, As, Sb A = N , P, P (〇), 〇As, As (〇), S b or S b R 1, R f and R 3 are the same or different, and are H, halogen, substituted and / or unsubstituted Academic group C η H 2 n + i, substituted and / or unsubstituted alkenyl having 1 to 18 carbon atoms and one or more double bonds, substituted and / or unsubstituted having 1 -1 8 carbon atoms and one or more alkynyl, substituted alkynyl, substituted And / or unsubstituted cycloalkyl C m Η 2 m _ i, _ one or more substituted and / or unsubstituted phenyl, or substituted and / or unsubstituted heteroaryl, A may contain K t may be contained in a cyclic or heterocyclic ring at multiple positions included in R 1, R 2 and / or R 3, and the groups attached to K t may be the same or different, where S Or Se, S, S (〇) 〇), 'S〇, Yiding paper size applicable to China National Standard (CNS) A4 specifications (210 x 297 mm) -16-A7 B7 $ 2774 ° >, invention Explanation (14) η 2 1-1 8, m 2 3-7, k 2 0 or 1-6, i 2 1 or 2 (for X 2 1), 1 2 1 (for x = 0), X 2 0 Or 1, y two 1 one 4. The method for preparing this compound is characterized in that the general formula is as follows: white metal salt d + -n (cf〇2, where D + is selected from alkali metals, which is reacted with a salt of general formula γ in a polar organic solvent

, [([R1 (CR2R3) 〇, A: <) yKt] + 'E where K t, A, R 1, R 2, R 3, k, 丄, χ, and y are as defined above, and —E is F —, Cl —, Br —, I —, BP4-, cl04 —, AsF6 —, SbF6 — or PF6 —. The compound according to the present invention may also be present in an electrolyte containing a compound of the formula such as τ. X- (CYZ) .- S〇2N (CR1R2R3) > This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ) (Please read the notes on the back before filling out this page); Binding and ordering printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -17, 527740 A7 B7 V. Invention Description (15) where X is Η, C 1 , C n F 2 η + 1, CnF2n-i or (Please read the notes on the back before filling this page) (SO 2). N (CR 1 R 2 R 3) 2, Y is H, F or C 1 , Z is H, F or C 1, R 1, R 2 and R 3 are H and / or alkyl, fluoroalkyl or cycloalkyl m is 0-9 and if X is bis, m total 0 η is 1 — 9 k is 0 Cm = 0) or k 2 1 (m = 1 — 9), which is prepared by reacting a partially or perfluorinated alkylsulfonium fluoride with dimethylamine in an organic solvent (DE 1 9 9 4 6 6 7 3). It is also possible to use an electrolyte containing a complex salt of the following formula (DE 199 51 8 0 4)

Mx + [EZ] y * x / y where X and y printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs are 1, 2, 3, 4, 5 or 6, and M x + is the metal ion E is the Lewis acid, Selected from BR 1 R 2 R 3, A 1 R 1 R 2 R: j, PR 1 R 2 R 3 R 4 R 5, A s R 1 R 2 R 3 R 4 R 5 and VR 1 R 2 R 3 R 4 R 5, R 1 to R 5 are the same or different, and are directly connected by single or double bonds as appropriate. Each of them has the following meanings alone or in combination: This paper size applies to Chinese National Standard (CNS) A4 (210X 297) Centimeters) 527740 A7 B7, which can pass F, C 1 or B r

〇S 0 2 R V. Description of the invention (16) Halogen (F, C 1 or B r ·) alkyl or alkoxy (Ci to C8 partially or completely substituted, square group ring, which is optionally by oxygen Linkages, including phenyl, naphthyl, enyl, and non-radical, which may be unsubstituted or mono- to hexa-substituted by a radical (c L-[8) or F, C 1 or B r, an aromatic heterocyclic ring Rings, which are optionally connected via oxygen, including pyridyl, pyrazolyl, and pyrimidinyl, which may be unsubstituted or mono-substituted to four by alkyl (ci_C8) or F, C 1 or B r Replaced by, B is 〇116, nr6r7, CR6R7R8, N (S〇2R6) (s 〇 2 R 7), (Please read the precautions on the back before filling this page)

(S 0 2 R 7) (S 0 2 R Intellectual Property Bureau of the Ministry of Economy a (Printed by Industrial and Consumer Cooperatives C (S 0 2 R 6, where R 6 to R, 8 are the same or different, depending on the circumstances Or double bonds are directly connected to each other, each alone or in combination, is hydrogen or as defined by R 1 to R 5 by the relevant boron or phosphorous Lewis acid / solvent adduct and bell or tetramethylene ammonium It can be obtained by the reaction of amine 'methylate or trifluoroformate. It can also have borate (DE 199 59 722) with the following formula:

Or oC〇R

1T Μχ + R3 R2 y- x / > Among which, the paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -19-527740 A 7 B7 5. Description of the invention (17) M is a metal ion or Tetraalkylammonium ions, X and y are 1, 2, 3, 4, 5, or 6, (Please read the precautions on the back before filling this page) Rule 1 to 1 ^ 4 are the same or different and are alkoxy Or carboxyl ((: 1 to (: 8), which may optionally be directly connected via single or double bonds. These acid salts are made from lithium tetraalkoxyborate or a 1: 1 mixture of lithium alkoxide and borate with the appropriate Group or carboxyl compound in an aprotic solvent at a ratio of 2: 1 or 4: 1. Additives, such as the silane compounds S i R 1 R 2 R 3 R 4 where R 1 to R 4 are Η

CyF 2y + l ~ * zHz 0 C y F 2 y + 1-z Η z. 〇C (〇) CyF2y + l- zHz 〇S 0 2 C y F 2 y + 1-z H z and 1 SX < 6 Printed by the Intellectual Property of the Ministry of Economic Affairs, Employee Consumer Cooperative 1 ^ 7 ^ 8 〇 ^ z ^ 2y + l, and R 1-R 4 are the same or different, and are aromatic rings, respectively, selected from phenyl and naphthyl. Replace or pass F, C v F 2 y-1-2 Η z, 〇C y F 2 y + 丄 一 ζ Η, 〇C (〇) C y F 2 v. 1-z H z ^ Paper size Applicable to China National Standard (CNS) A4 specification (2ωχ 297 public holidays) -20- 527740 A7 B7 V. Description of the invention (18) 〇S 0 2 c YF 2 y 11 1 2 Η z or N (cn F 2 n + i a 2 Η 2) 2 single or multiple substitutions, or, (please read the precautions on the back before filling this page), respectively, and each side is selected from the group consisting of Dk, _, and 卩, Which can be determined by F, Cy F 2 y + i-2 Η z, 〇Cy F 2 V + i —: Η 7 Ο C (Ο) C y F 2 y + 1 ~ ζ Η ζ Ν Ν 〇S 〇2 cy F 2 ”1-ζ Η 2 or M (c η F 2 η + i — ζ Η ζ) 2 mono- or polysubstituted (DE 100 2 7 6 26). The compounds according to the invention can also be used in Fluoroalkyl group-containing phosphate lithium electrolyte of the general formula

Lr [PFx (CyF2y + l-zHz) 6-x]-Among them, 1 ^ X 5 3 ^ y ^ 8 0 ^ z ^ 2y + l Printed coordination base (C y F 2 y + i-ζ Η z) may be the same or different, except for compounds of the general formula L 1 MPF a (CH b F c (; CF 3) d) e]-where a is 2 to 5 Integer, b = 0 or 1, c = 0 or 1, d = 2, and e is an integer from 1 to 4, but b and c are not 0 at the same time, the sum of a + e is 6, the ligand (CH b F. (CF 3) d) may be the same or different (DE 1008 9 5 5). Preparation method of lithium fluoroalkyl phosphate The paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297 mm) -21-527740 A7 B7_____ 5. The description of the invention (I9) is characterized by at least one of the following general compounds It is fluorinated by electrolysis in hydrogen fluoride, (please read the precautions on the back before filling this page) H rn P (C π Η 2 π + 1) · 3-m (. Melon) 〇P (C π Η 2 η, 1) 3 (TV) C 1 rn p (C η H 2 n + 丄) 3-m (. V) F m P (C η H 2 n + 1) 3-m (VI) C 1. P (C η H 2 n + i) 5-〇 (W) F. P (C η H 2 n + 1) 5-〇 (View), wherein 0 $ mS2, 3 $ n $ 8 'and 0S〇 € 4, the resulting fluorinated product mixture is extracted, phase separated and / or steamed ( It is better to separate by distillation. The obtained fluorinated alkylphosphorane (PhosPhorane) and lithium fluoride are reacted in an aprotic solvent or a solvent mixture under the condition of removing moisture, and purified and separated by conventional methods. The resulting salt. According to the present invention, the compound of the invention can also be used in electrolytes containing salts of the formula LUPiOR ^ aCOR ^ bCOR ^ cCOR ^ dFe] Printed by the Intellectual Property of the Ministry of Economic Affairs and the Employees' Cooperative, where 0 < a + b + c + dS5 a + b + c + d + e di 6, 1 ^ to 114 are alkyl, aryl or heteroaryl, respectively, and at least two of R1 to R may be directly connected to each other through a single or double bond (DE 1〇〇 16 801). These compounds are based on the following formula: Phosphorus CV) Compounds This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -22- 527740 A7 B7 V. Description of the invention (20) P (〇R1) a ( OR2) b (OR3) c (OR4) dFe where 〇 < a + b + c + d $ 5, a + b + c + d + e = 5, R 1 to R 4 are as defined above, and fluorinated Lithium is prepared by reacting in the presence of an organic solvent. There can also be an ionic liquid of the following formula in the electrolyte K + A-where K + is a cation selected from the following (please read the precautions on the back before filling this page) R1

R6 R1

N R3 R4 / R2

R5 " N R3 R4 Order d Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs R5

R4

R3 Among them, R 1 to R 5 are the same or different, and can be borrowed by single or double bond directly to each other. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -23- 527740 A7 _______B7 V. Description of the invention ( 2〇 Linked into, respectively, or: -Η, a halogen, (please read the notes on the back before filling this page)-alkyl (: C 1 to (: 8), which can be passed through other groups ( Let F, c 丄 NN (C n F 2 Π + 1-χ Η X) 2 ^ 〇 (C η F 2 η + 1-x Η χ), S 0 2 (C η F 2 η + 1 — χ Η X), C η F 2 η i _ χ Η χ is preferred, in which 1 &lt; η &lt; 6,0 &lt; X $ 13) is partially or completely substituted and is an anion selected from the group [BCOR ^ nCOR ^^ ORO ^ QR ^^-Among them, gn, m, 〇, and m + n + 〇 + p 2 4 Among them, R, 1 to R4 are the same or different, and can be directly connected by single or double bonds, each is or Combined with d, printed by the Ministry of Economic Affairs, Intellectual Property, and Industrial Cooperative Cooperative, aromatic rings selected from phenyl, naphthyl, enyl, or phenanthryl, which may be unsubstituted or substituted by C n F 2 η + 丄-X Η χ (where 1 &lt; η &lt; 6 and 〇 <χ &lt; 1 3) or (F, C 1, B r) mono- or poly-substituted, aromatic heterocyclic ring, selected from pyridyl, pyrazinyl or pyrimidinyl, which can be substituted by $ _ or by C n F 2 n + i-X Η χ (Wherein 1 &lt; η &lt; 6 and 〇, s 1 3) or halogen (F, C 1, B r) mono- or poly-substituted, or alkyl (C i to C 8), which may be passed through other groups Group (with F, ci, N (C n F 2 π + 1-Η X) 2, 0 (CnF'2n + i ~ xH "), 5 〇2 (C n F 2 n-L-H x) or C n F 2 n + 1-x H is the best paper size. Applicable to China National Standard (CNS) A4 specification (210X297 mm) -24- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 527740 A7 B7 V. Description of the invention (22) wherein 1 &lt; η &lt; 6, 0 &lt; XS 1 3) is partially or completely substituted, or each of OR 1 to OR 4 is or is combined to form an aromatic or aliphatic carboxyl group or a dicarboxyl group Oxosulfonyl or oxocarbonyl, other groups (as F, C 1, N (C n F 2 n + i-X 2 、 X) 2, 〇 (C η F 2 η + 1-x Η x), S 〇2 (C η F 2 η + 1-χ Η χ) or C η F · 2 η + i — χ Η χ is preferred, of which 1 &lt; η &lt; 6, 0 &lt; X ^ 13) Partial or complete substitution (DE 10 02 6 5 65). An ionic liquid K + A-(DE 10〇279 95) may also exist, where K + is the former defined and A-is an anion selected from the group [PFx (CyF2y + l-zHz) 6-x] 'Among them, 1 S χ &lt; 6 1 ^ y ^ 8, and 0Sz $ 2y + l 0 The compound according to the present invention may also exist in an electrolyte including a compound of the following formula: NR 1 R 2 R 3 wherein R1 And R2 are H, CvFsyTi-zH: or this paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)

-25- 527740 A7 B7 V. Description of the invention (23) (C n F 2 η-m H m) X, where X is aryl or heterocyclic group, and (Please read the precautions on the back before filling this page ) R 3 is (: C n F 2 η-m H m) Y, where Y is a heterocyclic group, or (C.F 2.-PH p) Z, where Z is an aryl group, and η therein , M, 〇, p, y, and ζ satisfy the following conditions: 0 ^ η ^ 6, 0 ^ m ^ 2 η, 2 ^ 〇 ^ 6, 0 ^ P ^ 2 〇, 1 S y $ 8, and 0 ^ z ^ 2 y + 1 to reduce the acid content of the aprotic electrolyte system in the electrochemical cell. It is also possible to use a win-based phosphate of the general formula

Mn + [PFx (CyF2y + l-zHz) 6-x] n 'Among them, printed by the Consumers ’Cooperative of Intellectual Property of the Ministry of Economic Affairs 1 ^ X ^ 6 1 ^ y ^ 8 0 ^ z ^ 2 y + 1 1 S n S 3, and M η τ is a monovalent to trivalent cation, especially: NR 丨 R2R3R4, PR! R2R3R4, this paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) -26-527740 A7 B7 V. Description of the invention (24) mNRiRW.RVh] (where k = 1-4, m = 〇-3, k + m ^ 4), (Please read the precautions on the back before filling this page) C (NR1R2 ) (NR3R4) (NR5R6), C (aryl) 3, R b or sulfonium ions, wherein R1 to R8 are H, alkyl or aryl (Ci — c3), which can pass through F, C 1 or B Partial substitution of r, wherein M n + includes Li +, na +, Cs +, K10 and Ag +. These fluoroalkyl phosphates can be obtained from the reaction of phosphane with fluoride or a fluoroalkyl phosphate metal salt with fluoride or chloride in an organic aprotic solvent (DE 1 0 0 3 8 8 58). This electrolyte may also include a mixture of the following a) at least one lithium fluoroalkyl phosphate Li + with the general formula Li + [PFx (CyF2y + l-zHz) 6-: &lt;] * where, 1 ^ X ^ 5 1 ^ y ^ 8 0 ^ z ^ 2y + l Each coordinator (cy F 2 y + 1-ζ Η z) printed by the consumer cooperative of the Intellectual Property Office of the Ministry of Economic Affairs may be the same or different, and b) at least one aggregation物 (D Ε 1005 8 2 6 4) 0 This electrolyte may also contain a silfluoroalkyl borate having the general formula

Mn + ([BR small) n This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) -27- 527740 A7 B7 V. Description of the invention (25) Among them, (Please read the precautions on the back before Fill in this page) Mn n + is a monovalent, divalent, or trivalent cation, and each ligand R is the same, which is (CXF 2 X +!), Where 1 SX $ 8, η 2, 1, 2 or 3 (DE 005 5 8 11). The production method of silfluoroalkyl borate is characterized in that at least one general formula is MnT ([B (CNhHn (where Mn + and η are as defined above) by reacting with at least one fluorinating agent in at least one solvent The obtained fluorinated compound is purified and isolated by a conventional method. The electrolyte may also include a borate having the following general formula:

Mn + [BFx (CyF2y + l-zHz) 4-x] n 'where 1 &lt; X &lt; 3, l $ y $ 8 and 〇SzS2y + l, and M is a monovalent to trivalent cation (1 S n S 3), but not the barium printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and the Ministry of Economic Affairs, 'especially: L 1, NR! R2R3R4, PR5R6R7RS, P (NR5R6) kR7mRVk-m (where k = 1-4, m = 0 — 3, k + m'4), or C (NR5R6) (NR7IT) (NR9R1Q), where R 丄 to R 4 are c YF 2 y + 1-2 H z, and this paper scale applies to China Standard (CNS) A4 specification (210X297 mm) -28- 527740 A7 B7 V. Description of invention (%) R5 to RiQ are Η or or square 方 cyclic cations, especially nitrogen and / or oxygen and / or sulfur Aromatic fluorene ring cation (DE 1 0 1 0 3 1 8 9). The method for preparing these compounds is characterized by: a) upon cooling, the BF 3 / solvent complex and the alkyl lithium react at a ratio of 1: 1, after slowly warming, removing most of the solvent, and then filtering the solid to a suitable solvent Rinse, or b) Lithium salt in a suitable solvent to react with b (CF 3) F 3 salt at a ratio of 1: 1. The mixture is stirred at elevated temperature, the solvent is removed, and the aprotic and non-aqueous solvent (for electrochemical cells) Preferably, it is added to the reaction mixture, and the mixture is dried, or c) B (CF 3) F 3 salt and lithium salt are reacted in water at an elevated temperature from 1: 1 to 1: 1 · 5 and boiled at Heat for 0.5 to 2 hours, remove water, add aprotic and non-aqueous solvents (preferably for electrochemical cells) to the reaction mixture, and dry the mixture. This electrolyte may also include a fluoroalkyl phosphate M of the general formula ([PFx (CyF2y + 1-2 Hz) 6-x] &quot;) n where. M η τ is a monovalent, divalent, or trivalent cation, 1 ^ X ^ 5, 1 ^ y ^ 8, 〇Sz $ 2y + l, n = 1, 2 or 3, each ligand (C y F 2 y + 1-: Η z) may be the same or different, M η + in fluoroalkyl phosphate is lithium ion. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page)

1. 1T Intellectual Property Bureau of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperatives-29- 527740 Α7 Β7) V. Description of the invention (27) ^ / 1 丁 （[? 匕 (〇? 3) 2]-), where + = (: 3+, eight taboo ten or 1 ^ minus ten ([? 卜 ((: 2? 5) 2]-), where "+ = 〇3 +

Ivr ([PF3 (C2F5) 3]-), where M + two Cs ten, K +, NaT, or one Cl one CC6H4) N2 +, MT ([PF.3 (C :, F7) 3r), Among them, M + = C s +, K +, Na a ten, to one C 1 (C 6 Η 4) Ν 2 + or to one 〇2 Ν (C 6 Η 4) Ν 2 ′ (DE 100 558 12) . The method for preparing fluorine-based phosphate is characterized in that at least one compound of the general formula HrP (CsH2s + l) 3-r, OP (CsH2s + i) 3,

ClrP (CsH2s + l) 3-r,

FrP (CsH2s + 1) 3-r,

CltP (CsH2s + 1) 5_r and / or FtP (CsH2§ + l) 5-r, of which 0 ^ r ^ 2, 3 S s S 8, and 0 ^ t ^ 4 are fluorinated in hydrogen fluoride , The obtained fluorinated reaction product mixture is separated, and the obtained fluorinated alkylphosphorane is reacted with the general formula M n + (F —) η in an aprotic solvent or a solvent mixture of anhydrous gas, wherein M η + and η are as before By definition, the resulting fluoroalkyl phosphate is purified and isolated in a conventional manner. The compound according to the present invention can be used in the electrolyte of an electrochemical cell. The anode material of the electrochemical cell here is a coated metal core (selected from the paper standard applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm). ) (Please read the notes on the back before filling this page} 、 Printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs -30-527740 Α7 Β7 V. Description of the invention (28) (Please read the notes on the back before filling (This page) sb, B 1, C d, I η, P b, Ga, and tin or their alloys) (DE 1006 〇 2 4). The method of producing this anode material is characterized by a) in A suspension or sol of a metal or alloy core made in urotropin, b) the suspension is emulsified with C 5 -C i 2 hydrocarbons, c) the emulsion is precipitated on the metal or alloy core, and d) the This system is heat-treated to convert metal hydroxides or oxyhydroxides into related oxides. The compound according to the present invention can also be used in the electrolyte of an electrochemical cell. The negative electrode of the electrochemical cell here is made of traditional lithium intercalation and intercalation compounds, or the cathode material is composed of lithium mixed oxide particles and subjected to one or more oxygen species. Metal oxide coating (DE 199 22 522). They can also consist of lithium mixed oxide particles coated with one or more polymers (D E 1 9 9 4 6 0 6 6). Similarly, the compounds according to the invention can also be used for negative electrodes made of lithium mixed oxide particles with one or more metal detection compounds and coatings of metal compounds (printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, DE 1001). 4 8 8 4). The method for preparing these materials is characterized by suspending particles in an organic solvent, adding an alkali metal salt compound suspended in the organic solvent, adding a metal oxonate dissolved in the solvent, adding a hydrolysis solution to the suspension, and then filtering In addition to the coated particles, the car is dried and calcined. Similarly, the compounds according to the present invention can be used for those containing positive electrode materials doped with oxides (.D E 1002 5 7 6 1). This positive electrode material is made from this paper. The Chinese standard (CNS) A4 specification (210 × 297 mm) -31-527740 A7 ___B7 _ V. Description of the invention (29) a) Add urea to the tin chloride solution, ( Please read the notes on the back before filling in this page) b) Add hexamethylenetetramine and appropriate compound to the solution, c) Emulsify the obtained sol in petroleum ether, d) Rinse the obtained gel and aspirate The solvent was removed, and e) the gel was dried and heated. Similarly, the compound according to the present invention can be used in a system containing less tin oxide in the negative electrode material (DE 1 0 2 5 7 6 2). This positive electrode material is made from a) adding urea to the tin chloride solution B) adding hexamethylenetetramine to the solution, c) emulsifying the obtained sol in petroleum ether, d) washing the obtained gel and removing the solvent by suction, e) drying and heating the gel, and f ) The obtained S η02 is exposed to a reducing gas flow in a ventilable furnace. The invention is explained in more detail below with examples. These examples serve to explain the invention but are not intended to limit the invention. Example printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Dou Example 1: Synthesis of perfluoro-1,2-bis (diethyltrifluorophosphate) ethane in a dry gas environment, 9.50 grams of solvent mixture (Ethylene carbonate: dimethyl carbonate: diethyl carbonate di 2: 2: 1 (weight ratio)) and 3.50 g (4.9 mmol) perfluoro-1,2-bis (di This paper scale applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) -32-527740 A7 B7 V. Description of the invention (30) Ethyl difluorophosphine) Ethane is added to the PFA container at room temperature. .44 grams (16. 9 millimoles) in L 1 F. The reaction mixture was stirred at room temperature for 3 hours until all the perfluoro-1,2-bis (diethyldifluorophospho) ethane was dissolved. Filter out excess LiF, containing 3.75 grams of perfluoro-1,2-bis (: diethyldifluorophosphate) ethanelithium (equivalent to a salt concentration of 28.3 in the electrolyte solution). % Or 0.48 mol / L) of mash (electrolyte) was analyzed by 19 F and 3 1 P-NMR spectra. Here, a special method (: CD: 3 C. OC D 3 membrane) was used to measure the spectrum of the pure electrolyte in a FE tube that was not diluted with other solvents. C C 1 3 F was used as the external reference for the membrane. With reference to the acetone-D 6 membrane, the frequencies of 85% Η 3 PO4 in water at 5 6 6 · 2 2 Η ζ were measured experimentally. The 19 F and 3 1 P N M R spectra were measured with a Bruker DRX 500 spectrometer (19 F is 47 6 · 6 Μ z, 3 1 P is 202 · 5 5 Η ζ). 1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. C Please read the French and Italian matters on the back first and fill out this order. 1 9 F ίΡ 3 1 Ρ Ν Μ R The spectrum shows that fluoride ion is between perfluorinated—1,2— Reaction of bis (diethyldifluorophosphine) ethane (starting molecule) with a perfluoroethyl or perfluoroethyl and perfluoroethyl bridge to form a perfluoro-1,2-bis (Diethyl trifluorophosphate) different stereoisomers of ethanedilithium salts. 2Li ^ [(C2F5) 2PF3 (CF2) 2PF3 (C2F5) 2] 2 'Isomer A (about 67%): 19F NMR: ~ 46.19dm (2F, 2PF); -87.57dm (4F, 2PF2) ; -82.2 8 m (6F, 2CF3); -82.42m (6F, 2CF3); -112.00dm (4F, 2CF2); This paper size applies Chinese National Standard (CNS) A4 specification (21 OX 297 mm) -33 527740 A7 B7 Intellectual Property of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperatives 5. Invention Description (31) -115.13dm (4F, 2CF2); -116.25dm (4F, 2CF2); J1P, F = 927Hz; J1p, f = 922Hz; J2p, F = 105Hz; J2p.F = 74Hz; J2p, f = 77Hz. 31P NMR &gt; 144.7qm Isomer B (about 33%): [! _F NMR &gt; 43.3 9dm (2F, 2PF) ; -87.7 3dm (4F? 2PF2); -80.38m (12F, 4CF3); -110.55dm (4F, 2CF〇; -115.70dm (8F, 4CF〇; J ,, F two 860Hz; JVf = 830Hz. &Quot; 1 PNMR: -14 4.8 qm Example 2: Synthesis of a mixture of perfluoro-1,2-bis (diethyltrifluorophosphate) ethane lithium and ginseng (pentafluoroethyl), lithium trifluorophosphate 9. 27 g of solvent mixture (ethylene carbonate: dimethyl carbonate: diethyl carbonate di 2: 2: 1 (weight ratio)) and 3. 39 g of perfluoro-1, 2-in a dry gas environment Bis (diethyldifluorophosphorus) A mixture of ethane (about 60 mole%) and ginseng (pentafluoroethyl) difluorophosphorane (about 40 mole%)] [This mixture is made from 1,2-bis (diethylphosphino) The electrochemical fluorination of ethane was used without further separation.] Added to 0.46 g (17.7 mmol) L 1 F in a PFA container at room temperature. The reaction mixture was stirred at room temperature. 3 hours until all perfluorinated starting materials are dissolved. Excess L 1 F is filtered off and contains 2.6 g of perfluoro-1,2-bis (.diethyldifluorophosphate) ethanedilithium (equivalent Yu Dian (Please read the notes on the back before filling this page):

, 1T — Λ, this paper size applies Chinese National Standard (CNS) A4 specification (2 丨 0 &gt; &lt; 297 mm) -34- 527740 Α7 Β7 V. Description of the invention (32) The salt concentration in the degrading solution is 〇 · 34 mol / L) and 1.0 g of ginseng (pentafluoroethyl) lithium trifluorophosphate (equivalent to a salt concentration of 0.23 ml / L in electrolyte solution) (electrolyte) 1 9 F and 3 1 P-NMR spectral analysis. The total concentration of salt in the electrolyte is 28.1%. Here, the spectrum was measured in the same manner as described in Example 1, and it was confirmed that two salts were present in the solution. 2Lr [(C2F5) 2PF3 (CF〇2PF3 (C2F5) 2] 2 • (about 60 mole%) llP NMR: -144.7am

Li + [(CiF5) 3PF3] · :: P NMR: -15Q.3am Example 3 of sinus: — (tetraethyl f female) full gas—1,2—bis (diethyldifluorophosphonate) ethane The synthesis of diC tetraethylammonium) perfluoro-1,2-bis (diethyltrifluorophosphate) ethane was carried out in a manner similar to that described in Example 1, but with anhydrous tetraethyl Ammonium fluoride replaces L 1 F. Analysis of 1 9 F and 3 1 P-N M R showed no sign of being an anion (please refer to Example 1). Example 4: Stability of oxidation reaction of perfluoro-1,2-bis (diethyltrifluorophosphate) ethane anion. Determination on platinum working electrode, lithium balance electrode and lithium reference electrode. This paper is applicable to China. Standard (CNS) Α4 specification (21〇297297) (Please read the precautions on the back before filling this page)

1T Intellectual Property Bureau of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperatives-35- 527740 A7 B7) 5. In the description of the invention (33), five ring diagrams are recorded. Here, the potential is first set from the rest potential to 10 millivolts. The rate of volts / second increased to 6 volts relative to L 1 / L 1 —, and then decreased to the resting potential. Electrolyte: 0.5 mol / kg ^ 丨 (m) perfluoro-1, 2-double (diethyl) Trifluorophosphate) ethanedilithium in EC / DMC (1: 1, ethylene carbonate / dimethyl carbonate). Measured oxidation potential &gt; 5 volts relative to Li / Li + [Please refer to Figure 1). Figure 1: The results shown in Figure 1 are obtained from the measurement cell of Example 4, and the ring spectrum was measured under the conditions described in this example, using perfluoro-1,2-bis (diethyltrifluorophosphate). ) Lithium ethane as a conductive salt. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized for China National Standard (CNS) A4 (210X 297 mm) -36-

Claims (1)

o This 8 8 8 8 ABCD r. 4 Years 6. Application for Patent Scope 1 Annex 2a: No. 901 33 1 10 Patent Application Chinese Application for Scope of Patent Amendment of the Republic of China 1991 Year 1 ◦ Month ^ 4th Amendment 1. A fluoroalkyl phosphate represented by the general formula (I), (Ma +) b [(Cn F2n + 1-mHm) yPF5-y (CRlR 2) xPF5-y (CnF2n + l-mHm) y] (I) where (Please read the precautions on the back before filling this page) c. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy, M a + 7E Valence, 2: Valence, or Trivalent Cation, a-1-2 or 3 ja — 1 for b = 2 ar = 3 for b = 2 and a = 2 for b = 1 for each case 1 η 8; η 2 for 1 or 2; 111 £ 111 2, 3 η 8 for 0 ^ m 4, 1 X 12, 〇y 2, wherein R 1 and R 2 are the same or different: selected from fluorine, hydrogen, C 1-8 fired fluorine C 1 · -8 alkyl and perfluoro C 1 -8 alkyl substituents j [tn The substituents in each case (C n F 2 η + 1-1 free H m) are the same or 1T This paper size applies Chinese National Standard (CNS) A 4 Specifications (210X297 mm) 527740 Α8 Β8 C8 D8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. The scope of patent application 2 is different. 2. The fluoroalkyl phosphate according to item 1 of the application, wherein the cation Ma + is an alkali metal cation. 3. The fluoroalkyl phosphate according to item 2 of the application, wherein the cation Ma + is a lithium, sodium or potassium cation. 4. The fluoroalkyl phosphate according to item 3 of the application, wherein the cation Ma + is a lithium cation. 5. The fluoroalkyl phosphate according to item 1 of the application, wherein the cation Ma + is a magnesium or aluminum cation. '6. The fluoroalkyl phosphate according to item 1 of the application, wherein M a + is an organic cation. 7. The fluoroalkyl phosphate according to item 6 of the application, wherein M a + is a nitrosyl cation, a nitrosyl cation or the general formula [N (R7) 4] +, [P (R7) 4 ] Organic cations of +, [P (N (R 7) 2) 4] + or [C (N (R 7) 2) 3] +, wherein the groups R 7 in each case are the same or different, and Is Η, Ci (Ci — Ci.) Or A, where any Η atom in the alkyl chain may be substituted with fluorine or aryl (containing heteroatoms as appropriate) or cycloalkyl, and / or alkyl The c atom in the chain can be replaced by a heteroatom. ‘8. The fluoroalkyl phosphate according to item 7 of the scope of the patent application, wherein the cycloalkyl group in the alkyl chain as a substituent of any fluorene atom has 5-6 members. 9. The fluoroalkyl phosphate according to item 7 in the scope of the patent application, wherein the C atom in the alkyl chain of the organic cation may be replaced by an oxygen atom. This paper size applies Chinese National Standard (CNS) Α4 specification (210 X 297) -2: '' -------— (Please read the notes on the back before filling in this I) 527740 A8 B8 C8 D8 VI. Patent application scope 3 1 10. The fluoroalkyl phosphate of item 6 of the patent application scope, wherein in each case, A is a 5- or 6-membered aryl group (which optionally contains Nitrogen and its phosphoryl hydrochloride hydrochloride items ο ο Group 1. Alkyl dicycloalkane or Fan ring} Commissioner of the Son of the Owner requested 6 oxygen or or such as 5 / · with and 1 is sulfur 1 A or, / medium The item of phosphoryl alkane hydrochloride hydrochloride ο No. IX. Nicotinic pyridine or Pyridoxine 2 is 1 A in IX Μ Π (Li Zhizhuan) The main formula Π Ⅲ η C formula • Tong 3 is its salt in K: Phosphorus ionylyangane fluoro ^ ^ No. 2 Kyoki item of P (Please read the precautions on the back before filling this page) + Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economics This paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -3-527740 A8 B8 C8 D8 4 Scope of patent application Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics R4R3 (Please read the precautions on the back before filling out this page) This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -4-527740 A8 B8 C8 DR 6. The scope of patent application 5 Among them, the groups Ri to R 6 in each case may be the same or different. When necessary, both of R 1 to R 6 are a fluorenyl group and a _ group (preferably a fluoro group) ) Or C: -8 alkyl, which may be optionally substituted by fc 丄, (Please read the precautions on the back before filling this page) N (CrF (2r + l- s) Hs) 2, 〇 (CrF ( 2 r + 1-s) H s), S ◦ 2 (cr F (2 …… H s) or cr b 2… —s) H s, where lSr $ 6 and 0SsS2r + i, where if The groups R 1 to R 6 are directly connected to the nitrogen, so the groups ri to R 6 are not halogen. 1 4 · The fluoroalkyl phosphate according to any one of claims 1 to 13 of the scope of patent application, wherein 1 $ η $ 6. 15. The fluoroalkyl phosphate according to item 14 of the scope of patent application, wherein 1 $ η $ 3. 16. The fluoroalkyl phosphate according to any one of claims 1 to 13 of the scope of patent application, wherein lgx ^ 8. 17 • The fluoroalkyl phosphates according to item 16 of the scope of patent application, of which 1 € X S 4. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 18 · If any of the fluoroalkyl phosphates in any of claims 1 to 13 of the scope of patent application, where m = 〇. 19 · The fluoroalkyl phosphate according to any one of claims 1 to 1.3 in the scope of patent application, wherein y is 2. 2 0. The fluoroalkyl phosphate according to any one of claims 1 to 13 of the scope of patent application, wherein R i and R 2 are fluorine. · 2 1 · If the fluoroalkyl phosphate in item 1 of the scope of the patent application, the paper size applies the Chinese National Standard (〇 阳) 8 4 specifications (210/297 Gong Chu) -5-527740 A8 B8 C8 D8 ____ Six Patent application scope 6 Formula (I) is (LrM (C2F5) 2PF3 (CF2) 2PF3 (C2F5) 2r2-) and (N (C2H5) 4 +) 2 [(C2F5) 2PF3 (CF2) 2PF3 (C2F5) 2] i2 ') 2 2 · —A method for preparing a fluoroalkyl phosphate according to any one of claims 1 to 21 of the scope of patent application, characterized in that at least one kind of fluorine-α, ω-bis [(fluorine Alkyl) fluorophosphino] alkane reacts with at least one fluorine salt of the general formula (X) (Ma +) [F '] a (X) wherein (M a +) and a are as described in claims 1 to 1 21 as defined in item 1 to obtain a fluoroalkyl phosphate of the general formula (I) as described in item 1 of the scope of the patent application, which is purified and / or isolated by conventional methods, as appropriate. 2 3 · The method according to item 22 of the scope of patent application, wherein the fluorine-α, ω-bis [(fluoroalkyl) fluorophosphino] ane is at least one compound of the general formula (XI) (CnF2n + l-mHm) yPF4-y (CRlR2) xPF4-y (CnF2n + l- mHm) y (XI) Among them, lSn $ 8, when n = 1 or 2, 0Sm € 2, this &amp; Zhang scale is applicable to Chinese National Standard (CNS) A4 specifications (2) 0 parent 297 mm 1 ^ 6-: (Please read the precautions on the back before filling out this page) Ordered by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs to print 527740 ABCD VI. Application for patent scope 7 crystals 3 $ For nS8, 0 $ ιτι $ 4; 1 $ χ $ ΐ2, 2, (Please read the notes on the back before filling out this page) where R i and R 2 are the same or different and are selected from fluorine, hydrogen, and c 1 — 8 alkyl, fluoro Ci-8 alkyl, and perfluoro c! -8 alkyl substituents, and in each case, the substituents (CnF2η + 1-mHm) are the same or different. 2 4 · The method of claim 22 in the scope of patent application No. 22, wherein the amount of the compound of general formula (X) in the scope of patent application No. 22 is an excess based on the amount of fluorine-ω-bis [(fluoroalkyl) fluorophosphine] alkane Up to 10 times. 2 5. Such as The method of claiming the 24th item in the patent scope, wherein the amount of the compound of the general formula (X) in the 22nd item of the patent application is an excess of up to 5 times based on the amount of fluorine-αω-bis [(fluoroalkyl) fluorophosphine] alkane 2 6 · If you apply for the method of item 25 in the patent scope, wherein the amount of the compound of the general formula (X) in the scope of application for the patent item 22 is fluorine- ^ ω-double [(fluorinyl) fluorophosphorus] The amount of excess is up to 2 times. 2 7 · The method according to item 22 of the patent application range, wherein the reaction with the compound of the general formula (X) in the item 22 of the patent application range is from 35 to + 80 °. C. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 2 8 · If the method of the scope of patent application No. 27, the reaction with the compound of the general formula (X) of the scope of patent application No. 22 It is carried out at a temperature of 20 to +50 ° C. 2 9 · The method according to item 28 of the patent application scope, wherein the reaction with the compound of general formula (X) in item 2 of the patent application scope table 22 is 10 to 25 t: at a temperature of.. 3 〇 As the method of patent application No. 22, where丨 used Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 527740 B8 C8 D8 6. Scope of patent application 8 The solvent is organic carbonate, organic ester, organic ether, organic ammonium, sulfur-containing solvent, aprotic solvent or at least part of the foregoing solvents A fluorinated derivative or a mixture of at least two of these solvents and / or fluorinated derivatives of these solvents. 31. The method of claim 30, wherein the solvent is an organic carbonate. 3 2 · The method according to item 31 of the scope of patent application, wherein the solvent is ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, or Methyl propyl carbonate. 33. The method of claim 30, wherein the solvent is an organic ester. 34. The method according to item 33 of the scope of patent application, wherein the solvent is methyl formate, ethyl formate, methyl acetate, ethyl acetate 'methyl propionate, ethyl propionate, methyl butyrate, Ethyl butyrate or r-butyrolactone. 35. The method of claim 30, wherein the solvent is an organic ether. 36. The method of claim 35, wherein the solvent is diethyl ether, dimethoxyethane, or diethoxyethane. 37. The method according to item 30 of the scope of patent application, wherein the solvent is organic amine 3 8. The method according to item 37 of the scope of patent application, wherein the solvent is dimethylformamide or dimethylformamide Ethylamine. 39. The method of claim 30 in the scope of patent application, wherein the solvent is a sulfur-containing solvent. ^ The paper size applies the Chinese National Standard (CNS) A4 specification (ΊΓο X 297 male thin): '(Please read the precautions on the back before filling in this page)-Installation · 1T 527740 A8 B8 C8 D8 VI. Application for patent scope 9 40. The method of claim 39, wherein the solvent is dimethylsulfinium, dimethylsulfide, diethylsulfide, or propionate. 41. The method of claim 30, wherein the solvent is an aprotic solvent. 42. The method of claim 41, wherein the solvent is acetonitrile, acrylonitrile, propionitrile, or acetone. 4 3 · A mixture, characterized in that it comprises a) at least one fluoroalkyl phosphate of general formula (I) as claimed in claims 1 to 21 of the patent application scope, and b) at least one polymer, which is propylene Homopolymers or copolymers of nitrile, vinylidene difluoride, methyl methacrylate, tetrahydrofuran, ethylene oxide, siloxane, and phosphazane or at least two of the foregoing homopolymers and / or copolymers A mixture comprising 5 to 90% by weight of component a) and 95 to 5% by weight of component b), said weight ratio being based on the sum of components a) and b). '4 4 · The mixture according to item 43 of the scope of the patent application, which comprises 100 to 80% by weight of component a) and 90 to 20% by weight of component b), said weight ratio is based on component a) and b) Sum. 45. The mixture according to item 43 of the scope of patent application, wherein component b) is a homopolymer or copolymer of vinylidene difluoride, acrylonitrile, methyl methacrylate or tetrahydrofuran. 46. The mixture according to item 45 of the patent application range, wherein component b) is a homopolymer or copolymer of vinylidene difluoride. -4 7 · If the mixture of item 43 in the scope of patent application, the paper size is t® (CNS) A4W ^ (210X297 ^ 7 (please read the precautions on the back before filling out this page)-equipment-、 1T Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-9-527740 ABCD κ, patent application scope 10 Polymers are at least partially cross-linked. 4 8. If a mixture of patent application scope No. 43 is included, it also contains At least one solvent. 4-9. The mixture according to item 18 of the scope of the patent application, wherein the solvent present is an organic carbonate, an organic ester, an organic ether, an organic amidine, a sulfur-containing solvent, an aprotic solvent, or at least one of the foregoing solvents Partially fluorinated derivatives or a mixture of at least two of these solvents and / or fluorinated derivatives of these solvents. 50. The method as claimed in claim 49, wherein the solvent is an organic carbonate. 5 1. The method according to item 50 of the scope of patent application, wherein the solvent is ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or Methyl propyl ester. 5 2. The method according to item 49 of the patent application, wherein the solvent is an organic ester. 5 3 · The method according to item 52 of the patent application, wherein the solvent is methyl formate. , Ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate or r-butyrolactone. 5 4 · If the scope of patent application is 4 9 The method according to item 5, wherein the solvent is an organic ether. 5 5 · The method according to item 54 of the scope of patent application, wherein the solvent is diethyl ether, dimethoxyethane, or diethoxyethane. 5 6 · If the method of the scope of patent application No. 49, wherein the solvent is organic ammonium amine. This paper size applies the Chinese National Standard (〇 Chan) 8.4 standard (210 \ 297 mm). 10: ： &quot; (Please read the notes on the back before filling out this page) One Pack · Order Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 527740 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics A8 B8 C8 _____ D8 VI. Application for Patent Scope 11 ^ 5 7 _If the method of applying for item 56 of the patent scope, t: _ 10, g Hai solvent is dimethylformamide or dimethylacetamide. 5 8. The method according to item 49 of the patent application scope: g: from ^ 110, the solvent is sulfur-containing Solvent. 5 9 · The method according to item 58 of the scope of patent application, wherein the solvent is dimethyl arylene, dimethyl sulfur, diethyl sulfur, or propidium. 6 0 · As the scope of patent application No. 4 9 The method of the above item, wherein the hydrazine solvent is an aprotic solvent. 61. The method of claim 60, wherein the solvent is acetonitrile, acrylonitrile, propionitrile, or acetone. 6 2 · Chloroalkyl phosphates according to any of claims 1 to 13 of the scope of patent application, used in electrolytes, primary batteries, accumulators, capacitors, ultracapacitors or jafani batteries. 6 3 · If it is a fluorinated phosphonate in item 62 of the patent application, it is used with other conductive salts and / or additives. 6 4 · The mixture of any one of items 43 to 49 in the scope of the patent application is used for electrolytes, primary batteries, accumulators, capacitors, supercapacitors or Jaffani batteries. 6 5 · If the mixture of item 64 in the patent application scope is used with other conductive salts and / or additives. '6 6. — An electrolyte comprising at least one fluoroalkyl phosphate as in any one of claims 1 to 21 or at least one as in any of claims 43 to 49 Of a mixture. 6 7 · If you apply for the electrolyte of item 6 of the patent scope, the scale of the electric book is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -11: ： ---- (Please read the back first Please note this page, please fill in this page) Order 527740 A8 B8 C8 D8 VI. Application for patent scope 12 The concentration of fluoroalkyl phosphate in the decomposition is 0.01 to 3 mol / liter, and 0.01 to 2 mol Per liter is preferred, particularly from 0.1 to 1.5 mol / liter. ^-(Please read the notes on the back before filling out this page) Order »Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210X297 mm)